Process for the production of unsaturated halogen compounds



United States Patent 7 2,991,316 PROCESS FOR THE PRODUCTION OF UNSATU- RATED HALOGEN COMPOUNDS Hans Disselnkiitter, Koln-Poll, and Peter Kurtz, Leverkusen-Bayerwerk, Germany, assignors to Far-benfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed May 2 3, 1957, Ser. No. 661,002 Claims priority, application Germany June 2'5, 1956 2 Claims. (Cl. 260654).

This invention relates to novel halogenated allyl-substituted proparyl alcohols, i.e., 12 and 1,3-dihalogenhexa-2,5-dienes and to a process for their production.

It is known that hydrogen chloride can be added to propargyl alcohol in the presence of mercury compounds, the hydrogen chloride only being added across the triple bond (cf. German patent specification No. 764,595). It has now been found that propargyl alcohol which is substituted in the 3-position by an allyl radical, which can if desired itself be substituted e.g. by alkyl groups, can be reacted with hydrogen halides with the formation of the corresponding halogenated allyl-substituted compound, i.e., 1,2- and 1,3-dihalogen-hexa-2,5- dienes.

The substituted propargyl alcohols can be reacted with the hydrogen halides, for example hydrogen chloride and hydrogen bromide, in manner known per se by introducing the hydrogen halide into the propargyl alcohol in the presence or absence of a solvent.

Examples of propargyl alcohols which can be used for the process of the invention, are hex-S-ene-Z-yne-l-ol, hept--ene-2Fyne-l-ol or 4-methyl-hex-5-ene-2Fyne-l-ol.

It is surprising that halogenated allyl-substituted propargyl alcohols, i.e., 1,2 and 1,3-dihalogen-hexa-2,5- dienes are obtained by the process of the invention while the double bond not attacked. Furthermore, bearing in mind the data given in the German patent specification No. 764,695, it is surprising that the alcoholic group is also esterified when using hydrogen chloride. The compounds obtained by the process of the invention can be used as intermediates or as nematodicides.

The following examples further illustrate the invention without limiting it thereto.

Example 1 Hydrogen chloride was introduced into 25 grams of hex-5-ene-2-yne-1-ol at a temperature of 60-80 C. for about 17 hours. The reaction product was then taken up in 100 milliliters of methylene chloride, the aqueous phase was separated out and the product obtained was distilled in vacuo. There were obtained 15.1 grams of 1,2- and 1,3-dichlorohexadiene-2,5. B.P. 55 C. at millimeters Hg, n 1.4896.

Example 2 Hydrogen chloride was introduced into a solution of 1 gram of mercuric chloride in 93.3 grams of hex-5- ene-Z-yne-l-ol preheated to 60 C., the hydrogen chloride being introduced until no more was absorbed. The temperature finally rose to 80 C. The reaction product was taken up in 300 milliliters of methylene chloride, the aqueous phase was separated out and dried over calcium chloride, and the product was distilled in vacuo. There were obtained 102.2 grams (=69.4%) of 1,2- and 1,3-dichlorohexadiene-2,5. B.P. 59 C.; (1 1.1156; n 1.4898.

Example 3 100 grams of hept-S-ene-Z-yne-l-ol were reacted as described in Example 2. The yield was 108.2 grams (=72.%) of 1,2.- and 1,3 dichloroheptadiene 2,5. B.P. =74 C.; 1 1.085 3; n 1.4912.

2 The eflicacy of thedichlor'ohexadiene and the-.dic'hl'oroheptadienewas tested-astollows: The compounds were dispersedjin water by 50% (referred to the'activesubstancwn of on the basis of a poly'glycol etheroftbenzyl-p hydroxydiphenyl which contained 12-45 glycol radicals in the molecule. Aphelenchoidesand meloidogyne were treated with this dispersion for 24 hours. lhereafiter the iollowing results were obtained:

killed animals in per- Concentration Aphelen- Meloldochoides gyne 1,2 and 1,3-diehlor0hexadiene. 96 8 38 1,2- and 1,3-dichloroheptadiene 988; 88 82 Example 4 Hydrogen bromide was introduced into a suspension of 0.2 g. of red mercuric oxide in 20 grams of hex-5- ene-2-yne-1-ol preheated to 60 C., the hydrogen bromide being introduced until no more was absorbed. The temperature rose to 65 C. The reaction products were worked up by distillation and provided 19.4 grams of 1,2- and 1,3 dibromohexadiene 2,5. (B.P. =83.585.5 C.; n =1.5485.)

Example 5 in which X is a member selected from the group consisting of hydrogen and methyl group, a hydrogen halide which is selected from the group consisting of hydrogen chloride and hydrogen bromide at a temperature between 60 and C. and recovering the 1,2- and 1,3-dihalogen in which X has the same meaning as above, from the reaction mixture.

2. The process according to claim 1, in which the reaction is carried out in the presence of a catalyst, which is a member selected from the group consisting of mercuric oxide and mercuric chloride.

(References on following page) UNITED STATES PATENTS Greenewalt Sept. 11, 1934 Engs et a1. Feb. 13, 1940 Bugs et a1. Apr. 28, 1942 Hearne et a1. Aug. 3, 1948 Anspon July 6, 1954 Anderegg et a1. Aug. 2, 1955 FOREIGN PATENTS Germany Nov. 2, 1953 OTHER REFERENCES Chemical Abstracts, vol. 44, column 7751(b), Sept. 10, 1950. 5 Chemical Abstracts, vol. 49,co1umn 8783(a), July Schmid et a1.: Chemical Abstracts, v01. 40 (1946), page 46704.

Nazarou: Chemical Abstracts, vol. 49 (1955), page 10 6847F. 

1. PROCESS FOR THE PRODUCTION OF UNSATURATED HALOGEN COMPOUNDS WHICH COMPRISES REACTING A COMPOUND OF GENERAL FORMULA 